CN113877585A - Almond-shaped hierarchical cerium-iron bimetal composite oxide and preparation method and application thereof - Google Patents
Almond-shaped hierarchical cerium-iron bimetal composite oxide and preparation method and application thereof Download PDFInfo
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- GSVIBLVMWGSPRZ-UHFFFAOYSA-N cerium iron Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Fe].[Ce].[Ce] GSVIBLVMWGSPRZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229960003350 isoniazid Drugs 0.000 claims abstract description 28
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 150000000703 Cerium Chemical class 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 16
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000004098 Tetracycline Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 229960002180 tetracycline Drugs 0.000 claims abstract description 7
- 229930101283 tetracycline Natural products 0.000 claims abstract description 7
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 7
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000000273 veterinary drug Substances 0.000 claims abstract description 3
- 239000002351 wastewater Substances 0.000 claims abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910052684 Cerium Inorganic materials 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- -1 cerium ions Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses an almond-shaped cerium-iron bimetal composite oxide, a preparation method and application thereof, wherein the bimetal composite oxide is a homogeneous high-dispersion almond-shaped hierarchical structure material, and the method comprises the following steps: preparing a cerium salt into an aqueous solution of the cerium salt; adding isoniazid solution into the cerium salt water solution, and then dropwise adding potassium ferrocyanide solution to form white precipitate; carrying out centrifugal separation, washing with deionized water and absolute ethyl alcohol on the precipitate, and drying to obtain a white complex precursor; and calcining the obtained precursor at controlled temperature, and naturally cooling to obtain the almond-shaped hierarchical cerium-iron bimetal composite oxide. The cerium-iron bimetal composite oxide can be used for photocatalytic degradation of tetracycline veterinary drug wastewater, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to an almond-shaped hierarchical cerium-iron bimetal composite oxide and a preparation method and application thereof.
Background
In the semiconductor material used as photocatalyst, CeO2Catalyst is due to oxidation-reduction of Ce4+/Ce3+There is a great deal of interest in having a large oxygen storage capacity so that more oxygen is available for the oxidation process. Especially CeO in the aspect of photocatalytic treatment of environmental pollution2Has remarkable effect of CeO2Can decompose organic substances which are difficult to decompose in the environment into CO2And H2O and other inorganic substances, and does not generate secondary pollution. However, since CeO2Inherent poor structural stability when Ce is used4+Reduction to Ce3+In which the crystal lattice always expands, CeO2This problem is ameliorated by combination with other metal oxides. Due to Fe2O3Has good stability in the catalytic process, high surface reactivity and magnetism, and is environment-friendly. Thus, CeO is added2With Fe2O3The combination can improve the activity and redox stability of the catalyst. In addition, the composition of Ce with a cheaper Fe oxide is also considered to be an economical method of reducing the use of a large amount of expensive rare earth metals. Therefore, the cerium-iron bimetal composite oxide material has potential application value in the field of photocatalysis. At present, researchers prepared some Fe by different methods such as a hydrothermal method, a sol-gel method and the like2O3And CeO2The nanometer composite material still has the defects of complex preparation method, poor dispersibility, difficult repeatability and the like of the composite material, and limits the application of the nanometer composite material in large-scale industrial production.
On the other hand, hierarchical structure materials with well-controlled morphology, compared to their bulk counterparts, have received much attention in recent years due to their large specific surface area, appropriate pore size distribution, and numerous active sites, having excellent adsorption, separation, and catalytic properties. For example, a hierarchical cerium-based oxide catalyst, a preparation method and use thereof (publication No. CN 105664917A), which forms CeO with a hierarchical structure by controllably adjusting the pH value in the preparation process to realize stepwise uniform precipitationx/MoO3-TiO2However, the composite material is expensive, and the dispersibility of the obtained material needs to be improved. Therefore, the development of a novel hierarchical cerium-based composite material and a preparation technology thereof are of great significance.
Disclosure of Invention
In view of the above, the present invention provides an almond-shaped hierarchical cerium-iron bimetal composite oxide, and a preparation method and an application thereof. Under the condition of room temperature, taking cerium salt and potassium ferrocyanide as a cerium source and an iron source, an isoniazide structure-oriented coordination agent and a solution acidity regulator, and deionized water as a solvent, and obtaining an almond-shaped cerium-iron bimetallic complex precursor at normal temperature and normal pressure; and then sintering the precursor under the temperature control condition to obtain the almond-shaped cerium-iron bimetal composite oxide with the hierarchical structure. The method has the advantages that the reaction condition is mild, the obtained almond-shaped hierarchical structure composite material has single appearance and good dispersibility, Ce and Fe in the composite are uniformly distributed, the process is simple, and the energy consumption is low; the cerium-iron bimetal composite oxide prepared by the method can be used in the field of photocatalytic degradation of organic pollutants.
The method specifically comprises the following steps:
step 1, dissolving cerium salt in water to prepare a cerium salt solution;
step 2, taking a certain amount of isoniazide to prepare an isoniazide solution, and pouring the isoniazide solution into a cerium salt solution;
step 3, dropwise adding a potassium ferrocyanide solution into the mixed solution under the condition of stirring to form a white precipitate; standing for 10 min, washing the precipitate for three times by centrifugal separation deionized water, washing for three times by absolute ethyl alcohol, and drying to obtain a white precursor;
and 4, placing the white precursor prepared in the step 3 in a crucible, calcining the white precursor in a temperature-controlled muffle furnace, and naturally cooling the calcined white precursor to obtain the almond-shaped hierarchical cerium-iron bimetallic oxide photocatalyst.
Further, the concentration of the cerium salt solution in the step 1 is 0.01-0.1 mol/L.
Further, the cerium salt solution in step 1 is a cerium nitrate aqueous solution.
Further, the concentration of isoniazide in the step 2 is 0.01-0.1mol/L, and the molar ratio of isoniazide to cerium salt is as follows: 1:1-3:1
Further, the temperature in the stirring condition in the step 2 is 20-25 ℃, the rotating speed is 350-800r/min, and the drying temperature is 40-80 ℃.
Further, in step 3, the concentration of the potassium ferrocyanide solution is 0.5mol/L, and the molar ratio of the cerium salt to the potassium ferrocyanide is 1:3-3: 1.
Further, the calcination temperature in step 4 is 400-800 ℃, the calcination time is 0.5-5 hours, and the heating rate is 1-5 ℃/min.
The invention also discloses application of the cerium-iron bimetallic oxide with the hierarchical structure prepared by the preparation method in photocatalytic degradation of tetracycline veterinary drug wastewater.
Compared with the prior art, the invention can obtain the following technical effects:
(1) the complex precursor is obtained by a one-step method, and is carried out at normal temperature and normal pressure without complex processes such as hydrothermal process and the like; the preparation process is simple, the production efficiency is high, and the energy consumption is low.
(2) The isoniazid added in the invention can be used as a structure directing agent on one hand, and can adjust the pH value of the solution on the other hand to promote the formation of the complex precursor.
(3) The conversion rate of the raw materials of the invention can reach more than 95 percent in terms of cerium.
(4) The cerium-iron bimetallic oxide prepared by the method has an almond-shaped hierarchical structure, wherein the Ce and Fe bimetallic oxides are highly uniformly dispersed, and the cerium-iron bimetallic oxide has excellent photocatalytic degradation performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD spectrum of a cerium-iron bimetal composite oxide having an almond-shaped hierarchical structure prepared in example 1 of the present invention. As can be seen, the composite material is a composite material containing CeO2、Fe2O3The bimetallic oxide of (1).
FIG. 2 is an SEM photograph of the hierarchical cerium-iron bimetallic oxide photocatalyst prepared in example 1 of the present invention. It can be seen that the resulting composite material is a cerium-iron bimetallic oxide with an almond-like hierarchical structure formed by aggregation of nano-small particles.
Fig. 3 is a Mapping graph of the cerium-iron bimetal oxide with a hierarchical structure prepared in example 1 of the present invention, and it can be seen that Ce and Fe elements in the material are highly dispersed.
FIG. 4 shows cerium of a hierarchical structure prepared in example 1 of the present inventionIron bimetallic oxide, commercial CeO2/Fe2O3(1: 1) mixture and commercial CeO2The performance diagram of the photocatalytic degradation of tetracycline. It can be seen that the cerium-iron bimetallic oxide with the hierarchical structure obtained by the method has excellent photocatalytic degradation performance on tetracycline, the degradation rate can reach 79 percent within 21 minutes, and the cerium-iron bimetallic oxide is obviously superior to CeO2/Fe2O3(1: 1) mixture and commercial CeO2。
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented. The application discloses a cerium-iron bimetal oxide with a hierarchical structure, and a preparation method and application thereof, wherein the preparation method comprises the following steps:
step 1, dissolving cerium salt in water to prepare a cerium salt solution;
step 2, weighing a certain amount of isoniazide to prepare an isoniazide solution, and pouring the isoniazide solution into a cerium salt solution to uniformly mix the isoniazide solution and the cerium salt solution;
step 3, dropwise adding a potassium ferrocyanide solution into the mixed solution under the condition of stirring to form white particle precipitates; standing for 10 min, washing the precipitate for three times by centrifugal separation deionized water, washing for three times by absolute ethyl alcohol, and drying to obtain a white precursor;
and 4, placing the white precursor prepared in the step 3 in a crucible, calcining at high temperature by using a temperature-controlled muffle furnace, and naturally cooling to obtain the almond-shaped hierarchical cerium-iron bimetallic oxide photocatalyst.
In the present production method, the first step of the method,
1. isoniazid added in the preparation process of the precursor has terminal amino groups and can coordinate with cerium ions and iron ions to form a bimolecular chelate, and the structure is oriented to cause the product to form an almond-shaped structure. If isoniazid is not added, potassium ferrocyanide and lanthanum directly form precipitates, and an almond-shaped appearance cannot be obtained. During the high-temperature calcination process, the ligand is decomposed to finally form the almond-shaped hierarchical cerium-iron bimetallic oxide.
2. The potassium ferrocyanide is a second ligand and can coordinate with cerium ions to generate precipitates. No precipitation occurred if no potassium ferrocyanide was added, and no precipitated product appeared.
Example 1
Dissolving a certain amount of cerium nitrate and isoniazid in deionized water to prepare 20mL of mixed aqueous solution containing 0.05mol/L of cerium nitrate and 0.05mol/L of isoniazid, and slowly adding 6mL of 0.5mol/L potassium ferrocyanide solution under the stirring condition of the rotating speed of 220 r/min and the temperature of 20 ℃. And carrying out centrifugal separation, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain a white precursor. And transferring the dried precursor sample into a crucible, sintering the precursor sample at high temperature by using a temperature-controlled muffle furnace, and keeping the temperature for 2 hours at the temperature of 500 ℃ at the temperature rise rate of 5 ℃/min to obtain a product. The XRD spectrum of the obtained product is shown in figure 1, and the scanning electron micrograph and the element analysis mapping graph of Ce, Fe and O are shown in figures 2 and 3. The performance of the prepared cerium-iron bimetallic oxide as a photocatalyst for degrading tetracycline is shown in figure 4, and the degradation rate of tetracycline reaches 79 percent after the reaction is carried out for 21 minutes under the condition of visible light.
Example 2
Dissolving a certain amount of cerium nitrate and isoniazid in deionized water to prepare 20mL of mixed aqueous solution containing 0.25mol/L of cerium nitrate and 0.5mol/L of isoniazid, and slowly adding 6mL of 0.5mol/L potassium ferrocyanide solution under the stirring condition of the rotating speed of 200 r/min and the temperature of 25 ℃. And carrying out centrifugal separation, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain a white precursor. And transferring the dried precursor sample into a crucible, sintering the precursor sample at high temperature by using a temperature-controlled muffle furnace, wherein the heating rate is 5 ℃/min, and keeping the temperature for 0.5 hour at 600 ℃ to obtain a product.
Example 3
Dissolving a certain amount of cerium nitrate and isoniazid in deionized water to prepare 20mL of mixed aqueous solution containing 0.25mol/L of cerium nitrate and 0.75mol/L of isoniazid, and slowly adding 8mL of 0.5mol/L potassium ferrocyanide solution under the stirring condition of the rotating speed of 520 r/min and the temperature of 20 ℃. And carrying out centrifugal separation, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain a white precursor. And transferring the dried precursor sample into a crucible, sintering the precursor sample at high temperature by using a temperature-controlled muffle furnace, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1 hour at 400 ℃ to obtain a product.
Example 4
Dissolving a certain amount of cerium nitrate and isoniazid in deionized water to prepare 20mL of mixed aqueous solution containing 0.10mol/L of cerium nitrate and 0.15 mol/L of isoniazid, and slowly adding 10mL of 0.5mol/L potassium ferrocyanide solution under the stirring condition of the rotating speed of 320 r/min and the temperature of 20 ℃. And carrying out centrifugal separation, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 60 ℃ to obtain a white precursor. And transferring the dried precursor sample into a crucible, sintering the precursor sample at high temperature by using a temperature-controlled muffle furnace, wherein the heating rate is 5 ℃/min, and keeping the temperature for 1 hour at 400 ℃ to obtain a product.
While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method is characterized in that the obtained cerium-iron bimetal composite oxide is a homogeneous and highly dispersed almond-shaped hierarchical structure material, and the preparation method comprises the following steps:
step 1, dissolving cerium salt in water to prepare a cerium salt solution;
step 2, weighing a certain amount of isoniazide, dissolving the isoniazide in water to obtain an isoniazide solution with a certain concentration, and then mixing the isoniazide solution with a cerium salt solution;
step 3, dropwise adding a potassium ferrocyanide solution into the mixed solution to form white particle precipitates; standing for 10 min, washing the precipitate for three times by centrifugal separation deionized water, washing for three times by absolute ethyl alcohol, and drying to obtain a white complex precursor;
and 4, placing the white precursor prepared in the step 3 in a crucible, calcining the white precursor in a temperature-controlled muffle furnace, and naturally cooling to obtain the almond-shaped hierarchical cerium-iron bimetal composite oxide.
2. The almond-shaped hierarchical cerium-iron bimetal composite oxide of claim 1, wherein the concentration of the cerium salt solution in the step 1 is 0.01-0.6 mol/L cerium nitrate aqueous solution.
3. The almond-shaped hierarchical cerium-iron bimetal composite oxide and the preparation method thereof according to claim 1, wherein the concentration of isoniazid in step 2 is 0.01-0.1mol/L, and the molar ratio of isoniazid to cerium salt is: 1:1-3:1.
4. The almond-shaped hierarchical cerium-iron bimetal composite oxide and the preparation method thereof as claimed in claim 1, wherein the temperature in the stirring condition in step 3 is 20-25 ℃, the rotation speed is 180-220 r/min, and the drying temperature is 40-80 ℃.
5. The almond-shaped hierarchical cerium-iron bimetal composite oxide and the preparation method thereof according to claim 1, wherein the concentration of the potassium ferrocyanide solution in the step 3 is 0.5mol/L, and the molar ratio of the cerium salt to the potassium ferrocyanide is 1:3-3: 1.
6. The almond-shaped hierarchical cerium-iron bimetal composite oxide and the preparation method thereof as claimed in claim 1, wherein the calcination temperature in the step 4 is 400-700 ℃, the calcination time is 0.5-5 hours, and the temperature rise rate is 1-5 ℃/min.
7. An almond-shaped hierarchical cerium-iron bimetal composite oxide, characterized in that it is prepared by the preparation method of any one of claims 1 to 6.
8. The use of the almond-shaped hierarchical cerium-iron bimetallic composite oxide of claim 7 in visible light photocatalytic degradation of tetracycline veterinary drug wastewater.
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| CN106496284A (en) * | 2016-10-18 | 2017-03-15 | 四川理工学院 | A kind of isonicotinoyl hydrazone nickel complex photocatalyst and its preparation method and application |
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| CN110787842A (en) * | 2019-11-12 | 2020-02-14 | 杭州鼎好新材料有限公司 | Photocatalyst for photocatalytic degradation of formaldehyde and preparation method thereof |
| US20210139348A1 (en) * | 2019-11-13 | 2021-05-13 | King Fahd University Of Petroleum And Minerals | Activated carbon-iron/cerium oxide nanocomposite suitable for dye removal |
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